Thermoplastic elastomer laminates and glass run channels molded therefrom

ABSTRACT

According to the present invention, there is provided a thermoplastic elastomer laminate which comprises 
     a layer comprising a thermoplastic elastomer (A) composed of a crystalline polyolefin and a rubber, and 
     a layer comprising an ultra-high molecular weight polyolefin (B) or an ultra-high molecular weight polyolefin composition. 
     In addition, a glass run channel composed of the thermoplastic elastomer laminate is also provided in the invention.

FIELD OF THE INVENTION

This invention relates to thermoplastic elastomer laminates effectivelyuseful in preparing interior automotive trims and sealing materials, andto glass run channels molded from said laminates, and more particularlyto thermoplastic elastomer laminates consisting of a base layer made ofthermoplastic elastomer and a surface layer made of lubricant resin, andto glass run channels having a window glass sliding portion composed ofsaid laminates.

BACKGROUND OF THE INVENTION

Various laminates have heretofore been used for preparing interiorautomotive trims, sealing materials or the like. For Example, glass runchannel is known as one of important sealing materials used inautomobile. This glass run channel is a guide member provided between awindow glass and a window frame in order to make an intimate (liquidtight) sealing operation between the window glass and the window framepossible while facilitating the ascent-decent and open-shut operationsof the window glass.

Materials used conventionally for preparing glass run channels include(1) a composite material comprising vulcanized rubber consistingessentially of an ethylene/propylene/diene copolymer rubber excellent inweathering resistance and heat resistance, an adhesive and nylon fiber,(2) a composite material comprising the above-mentioned vulcanizedrubber and an adhesive, and (3) a non-rigid PVC for use in contourextrusion.

The conventional glass run channels composed of such composite materialsas mentioned above comprise a main body having a groove-likecross-section and tongue-like draining portions, each extending from thetip of the side wall of groove toward the central side of the groove.

In the conventional glass run channels, a nylon film or the like islaminated with an adhesive to the surface of the window glass slidingportion of each draining portion in order that the window glass may partfavorably from said sliding portion and also may be prevented fromstaining, or the surface of each sliding portions of the drainingportions is subjected, before or after the above-mentioned lamination ofthe nylon film or the like, to embossment treatment in order to lessenthe contact area of said sliding portions with the window glass.

In a process of preparing such glass run channels as mentioned above,however, there are involved such inconveniences as large number of stepsand time-consuming jobs, wherein because of no adhesive propertiesexisting between the above-mentioned non-rigid synthetic resin orvulcanized rubber and such surface material as nylon, it becomesnecessary to take the steps of coating the surface of the window glasssliding portions of the main body of glass run channel molded from theabove-mentioned non-rigid synthetic resin or vulcanized rubber with anadhesive, and laminating a nylon film or the like to the surface of saidwindow glass sliding portions, and further to carry out the embossmenttreatment of the surface of said sliding portion before or after theabove-mentioned lamination of the nylon film or the like.

On one hand, when the conventional glass run channels are prepared bycontour extrusion molding the above-mentioned composite material (3),i.e. a non-rigid polyvinyl chloride, the production process employedtherefor is simplified. However, this composite material is poor in heatresistance and dimensional stability, and is inferior in practicalperformance to the above-mentioned composite materials (1) and (2).

When the conventional glass run channels molded from the above-mentionedcomposite materials (1) or (2), there is a durability problem of thechannels because the nylon film or the like is laminated by means of anadhesive to the window glass sliding portions of the draining portions,and there is also such a drawback that the thus laminated nylon film isliable to peel off from said window glass sliding portions with time andupon exposure outdoors. Furthermore, the embossed pattern formed on thesurface of the window glass sliding portions by the embossment treatmentis not fully satisfactory in point of combination of fineness anduniformity, and there is much room for improvement in intimatecontacting properties between the window glass sliding portion and thewindow glass at the time of shutting the window glass and also in lightsliding properties between the window glass sliding portions and thewindow glass at the time of opening the window glass.

Accordingly, there has been desired the advent of laminates which areexcellent in weathering resistance, heat resistance and dimensionalstability, can be prepared by a simplified production process and can beused for the purposes such as interior automotive trims, sealingmaterials or the like, and also the advent of glass run channelscomprising window glass sliding portions molded from said laminates.

OBJECT OF THE INVENTION

The present invention is intended to solve such problems associated withthe prior art as mentioned above, and an object of the invention is toprovide thermoplastic elastomer laminates excellent in weatheringresistance, heat resistance and dimensional stability, which can also beprepared by a simplified production process and are excellent inso-called economical efficiency.

A further object of the invention is to provide glass run channels whichare excellent not only in economical efficiency but also in durability,intimate contacting properties with the window glass at the time ofshutting the window glass and in easy sliding properties with the windowglass at the time of opening the window glass.

SUMMARY OF THE INVENTION

The first thermoplastic elastomer laminates of the present inventioncomprises a layer comprising a thermoplastic elastomer (A) composed of acrystalline polyolefin and a rubber, and a layer comprising anultra-high molecular weight polyolefin (B).

The thermoplastic elastomer (A) referred to above preferably includesthose obtained by subjecting a mixture comprising 70-10 parts by weightof a crystalline polypropylene (a) and 30-90 parts by weight of rubber(b) which is ethylene/propylene copolymer rubber or anethylene/propylene/diene copolymer rubber (the sum total of thecomponents (a) and (b) is 100 parts by weight) to dynamic heat treatmentin the presence of organic peroxide, said rubber (b) being partiallycross-linked.

The ultra-high molecular weight polyolefin (B) referred to abovepreferably has an intrinsic viscosity [μ], as measured in decalin at135° C., of 10-40 dl/g.

The second thermoplastic elastomer laminates of the invention comprisesa layer comprising a thermoplastic elastomer (A) composed of acrystalline polyolefin and rubber, and a layer comprising an ultra-highmolecular weight polyolefin composition (C), said ultra-high molecularweight polyolefin composition consisting essentially of an ultra-highmolecular weight polyolefin having an intrinsic viscosity [η], asmeasured in decalin at 135° C., of 10-40 dl/g, and polyolefin having anintrinsic viscosity [η], as measured in decalin at 135° C., of 0.1-5dl/g, said ultra-high molecular weight polyolefin existing in aproportion of 15-40% by weight based on 100% by weight of the sum totalof the ultra-high molecular weight polyolefin and polyolefin, and saidultra-high molecular weight polyolefin composition (C) having anintrinsic viscosity [η], as measured in decalin at 135° C., of 3.5-8.3dl/g.

The above-mentioned thermoplastic elastomer (A) is the same as used inthe first thermoplastic elastomers of the invention.

The aforesaid ultra-high molecular weight polyolefin composition (C) maycontain 1-20% by weight, based on the composition (C), of a liquid orsolid lubricant.

The third thermoplastic elastomer laminates of the invention comprises alayer comprising a graft-modified thermoplastic elastomer (GA) and alayer comprising an ultra-high molecular weight polyolefin (B), saidgraft-modified thermoplastic elastomer (GA) being obtained by dynamicheat treatment and partial cross-linkage of a blend in the presence ofan organic peroxide, said blend containing (i) 95 -10 parts by weight ofa peroxide cross-linking olefin copolymer rubber, (ii) 5-90 parts byweight of a polyolefin (the sum total of the (i) and (ii) components is100 parts by weight) and (iii) 0.01-10 parts by weight of anα,β-unsaturated carboxylic acid or its derivatives, or an unsaturatedepoxy monomer.

The graft-modified thermoplastic elastomer (GA) referred to abovepreferably includes those further containing (iv) 5-100 parts by weightof a peroxide non-cross linking rubbery substance and/or (v) 3-100 partsby weight of a mineral oil softener based on 100 parts by weight of thesum total of the components (i) and (ii).

In the graft-modified thermoplastic elastomer (GA) mentioned above, itis desirable that the content of the peroxide cross-linking olefincopolymer rubber (i) is 95-60 parts by weight and that of the polyolefin(ii) is 5-40 parts by weight (the sum total of the components (i) and(ii) is 100 parts by weight).

The ultra-high molecular weight polyolefin (B) used herein is the sameas used in the first thermoplastic elastomer laminates of the invention.

The fourth thermoplastic elastomer laminates of the invention comprisesa layer comprising a graft-modified thermoplastic elastomer (GA) and alayer comprising an ultra-high molecular weight polyolefin composition(C), said graft-modified thermoplastic elastomer (GA) being obtained bydynamic heat treatment and partial cross-linkage of a blend in thepresence of an organic peroxide, said blend containing (i) 95-10 partsby weight of a peroxide cross-linking olefin copolymer rubber, (ii) 5-90parts by weight of a polyolefin (the sum total of the (i) and (ii)components is 100 parts by weight) and (iii) 0.01-10 parts by weight ofan α,β-unsaturated carboxylic acid or its derivatives, or an unsaturatedepoxy monomer, said ultra-high molecular weight polyolefin composition(C) consisting essentially of an ultra-high molecular weight polyolefinhaving an intrinsic viscosity [η], as measured in decalin at 135° C., of10-40 dl/g and a polyolefin having an intrinsic viscosity [η], asmeasured in decalin at 135° C., of 0.1-5 dl/g, said ultra-high molecularweight polyolefin existing in a proportion of 15- 40% by weight based on100% by weight of the sum total of the ultra-high molecular weightpolyolefin and polyolefin, and said ultra-high molecular weightpolyolefin composition (C) having an intrinsic viscosity [η], asmeasured in decalin at 135° C., of 3.5-8.3 dl/g.

The graft-modified thermoplastic elastomer (GA) used herein preferablyincludes the same as used in the third thermoplastic elastomer laminatesof the invention.

In the graft-modified thermoplastic elastomer (GA) mentioned above, itis desirable that said elastomer (GA) contains 95-60 parts by weight ofthe aforesaid peroxide cross-linking olefin copolymer rubber (i) and5-40 parts by weight of the aforesaid polyolefin (ii) (the sum total ofthe components (i) and (ii) is 100 parts by weight).

The ultra-high molecular weight polyolefin composition (C) used hereinmay contain 1-20% by weight of a liquid or solid lubricant based on thecomposition (C).

The first glass run channel of the present invention comprises a mainbody having a groove-like cross-section and tongue-like drainingportions extending from the tip of side wall of the groove toward thecentral side of said groove, portions of said glass run channel to be incontact with the window glass comprising a layer of a thermoplasticelastomer (A) composed of a crystalline polyolefin and a rubber and alayer of an ultra-high molecular weight polyolefin (B), said ultra-highmolecular weight polyolefin (B) layer being designed so as to be incontact with the window glass, and said ultra-high molecular weightpolyolefin (B) having an intrinsic viscosity [η], as measured in decalinat 135° C., of 10-40 dl/g.

The thermoplastic elastomer (A) used herein preferably includes those asdefined in the first thermoplastic elastomer laminates of the presentinvention.

The second glass run channel of the invention comprises a main bodyhaving a groove-like cross-section and tongue-like draining portions,each extending from the tip of side wall of the groove toward thecentral side of said groove, portions of said glass run channels to bein contact with the window glass comprising a layer of a thermoplasticelastomer (A) composed of a crystalline polyolefin and rubber and alayer of an ultra-high molecular weight polyolefin composition (C), saidlayer of the ultra-high molecular weight polyolefin composition (C)being designed so as to be in contact with the window glass, saidultra-high molecular weight polyolefin composition (C) consistingessentially of an ultra-high molecular weight polyolefin having anintrinsic viscosity [η], as measured in decalin at 135° C., of 10-40dl/g and a polyolefin having an intrinsic viscosity [η], as measured indecaline at 135° C., of 0.1-5 dl/g, said ultra-high molecular weightpolyolefin existing in a proportion of 15- 40% by weight based on 100%by weight of the sum total of the ultra-high molecular weight polyolefinand the polyolefin, and said ultra-high molecular weight polyolefincomposition (C) having an intrinsic viscosity [η], as measured indecalin at 135° C., of 3.5-8.3 dl/g.

The thermoplastic elastomer (A) used herein preferably includes those asdefined in the first glass run channel of the present invention.

The above-mentioned ultra-high molecular weight polyolefin composition(C) may contain 1-20% by weight, based on the composition (C), of aliquid or solid lubricant.

The third glass run channel of the invention comprises a main bodyhaving a groove-like cross-section, and tongue-like draining portionsextending from the tip of side wall of the groove toward the centralside of said groove, portions of said glass run channel to be in contactwith the window glass comprising a layer of a graft-modifiedthermoplastic elastomer (GA) and a layer of an ultra-high molecularweight polyolefin (B), said layer of the ultra-high molecular weightpolyolefin (B) being designed so as to be in contact with the windowglass, said graft-modified thermoplastic elastomer (GA) being obtainedby dynamic heat treatment and partial cross-linkage of a blend in thepresence of organic peroxide, said blend containing (i) 95-10 parts byweight of a peroxide cross-linking olefin copolymer rubber, (ii) 5-90parts by weight of a polyolefin (the total sum of the components (i) and(ii) is 100 parts by weight), and (iii) 0.01-10 parts by weight of anα,β-unsaturated carboxylic acid or its derivative, or an unsaturatedepoxy monomer, and said ultrahigh molecular weight polyolefin (B) havingan intrinsic viscosity [η], as measured in decalin at 135° C., of 10-40dl/g.

The fourth glass run channel of the invention comprises a main bodyhaving a groove-like cross-section, and tongue-like draining portionsextending from the tip of side wall of the groove toward the centralside of said groove, portions of said glass run channel to be in contactwith the window glass comprising a layer of a graft-modifiedthermoplastic elastomer (A) and a layer comprising an ultra-highmolecular weight polyolefin composition (C), said layer of theultra-high molecular weight polyolefin composition (C) being designed soas to be in contact with the window glass, said graft-modifiedthermoplastic elastomer (GA) being obtained by dynamic heat treatmentand partial cross-linkage of a blend in the presence of organicperoxide, said blend containing (i) 95-10 parts by weight of a peroxidecross-linking olefin copolymer rubber, (ii) 5-90 parts by weight of apolyolefin (the sum total of the (i) and (ii) components is 100 parts byweight) and (iii) 0.01-10 parts by weight of an α,β-unsaturatedcarboxylic acid or its derivative, or an unsaturated epoxy monomer, saidultra-high molecular weight polyolefin composition (C) consistingsubstantially of an ultra-high molecular weight polyolefin having anintrinsic viscosity [η], as measured in decalin at 135° C., of 10-40dl/g and a polyolefin having an intrinsic viscosity [η], as measured indecalin at 135° C., of 0.1-5 dl/g, said ultra-high molecular weightpolyolefin existing in a proportion of 15-40% by weight based on the sumtotal of the ultra-high molecular weight polyolefin and the polyolefin,and said ultra-high molecular weight polyolefin composition (C) havingan intrinsic viscosity [η], as measured in decalin at 135° C., of3.5-8.3 dl/g.

The ultra-high molecular weight polyolefin composition (C) used hereinmay contain 1-20% by weight, based on the composition (C), of a liquidor solid lubricant.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sectional view of a glass run channel of the presentinvention.

FIG. 2 is an enlarged sectional view of a portion of the glass runchannel shown in FIG. 1, with which the window glass comes into contact.

FIG. 3 is a view showing how the glass run channel is fitted to theautomobile's door.

FIG. 4 is a cross-sectional view of the fitted glass run channel showingits state at the time when the window glass is open.

FIG. 5 is a cross-sectional view of the fitted glass run channel showingits state at the time when the window glass is shut.

DETAILED DESCRIPTION OF THE INVENTION

The thermoplastic elastomer laminates and glass run channels molded fromsaid laminates according to the present invention are illustrated belowin detail.

First, the thermoplastic elastomer laminates of the invention areillustrated.

The thermoplastic elastomer laminates of the invention are dividedroughly into the following four categories.

The first thermoplastic elastomer laminates of the invention comprise alayer of a specific thermoplastic elastomer (A) and a layer of anultra-high molecular weight polyolefin (B).

The second thermoplastic elastomer laminates of the invention comprise alayer of a specific thermoplastic elastomer (A) and a layer of aspecific ultra-high molecular weight polyolefin composition (C).

The third thermoplastic elastomer laminates of the invention comprise alayer of a specific graft-modified thermoplastic elastomer (GA) and alayer of a specific ultra-high molecular weight polyolefin (B).

The fourth thermoplastic elastomer laminates of the invention comprise alayer of a specific graft-modified thermoplastic elastomer (GA) and alayer of a specific ultra-high molecular weight polyolefin composition(C).

Thermoplastic Elastomer (A)

The thermoplastic elastomer (A) used in the first and secondthermoplastic elastomer laminates of the invention is composed of acrystalline polyolefin and a rubber.

The crystalline polyolefin used in the invention includes homopolymersor copolymers of α-olefin having 2-20 carbon atoms.

Concrete examples of the crystalline polyolefin used herein include such(co)polymers as listed below.

(1) Ethylene homopolymer (a low-pressure polyethylene, a high-pressurepolyethylene)

(2) Copolymers of ethylene and not more than 10 mol% of other α-olefinor vinyl monomer such as vinyl acetate, ethyl acrylate or the like

(3) Propylene homopolymer

(4) Random copolymers of propylene and not more than 10 mol% of otherα-olefin

(5) Block copolymers of propylene and not more than 30 mol% of otherα-olefin

(6) Homopolymer of 1-butene copolymers of 1-butene and not more than

(7) Random copolymers of 1-butene and not more than 10 mol% of otherα-olefin

(8) Homopolymer of 4-methyl-1-pentene more than 20 mol% of otherα-olefin

The other α-olefin used in the copolymers exemplified above includesconcretely ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene,1-octene, etc.

The rubber used in the invention, though not particularly limited,includes preferably olefin copolymer rubbers.

The olefin copolymer rubbers mentioned above are amorphous, random andelastic copolymers derived from α-olefins, having 2-20 carbon atoms,including amorphous α-olefin copolymers derived from 2 or moreα-olefins, and α-olefin/non-conjugated diene copolymers derived from 2or more α-olefins and non-conjugated diene.

Concrete examples of such olefin copolymer rubbers as used hereininclude rubbers as listed below.

(1) Ethylene/α-olefin copolymer rubber [ethylene/α-olefin (molarratio)=about 90/10-50/50]

(2) Ethylene/α-olefin/non-conjugated diene copolymer rubber[ethylene/α-olefin (molar ratio)=about 90/10-50/50]

(3) Propylene/α-olefin copolymer rubber

[propylene/α-olefin (molar ratio)=about 90/10-50/50]

(4) Butene/α-olefin copolymer rubber

[Butene/α-olefin (molar ratio)=about 90/10-50/50]

The above-mentioned α-olefin used in these copolymer rubbers includesthe same examples of α-olefins as used in constituting the aforesaidcrystalline polyolefin to be contained in the thermoplastic elastomer(A).

The non-conjugated diene used in the above-mentioned copolymer rubbersincludes concretely dicyclopentadiene, 1,4-hexadiene, cyclooctadiene,methylene norbornene, ethylidene norbornene, etc.

The copolymer rubbers exemplified above preferably have a Mooneyviscosity ML₁₊₄ (100° C.) of 10-250, especially 40-150, and preferablyhave an iodine value of not more than 25 when they are copolymerizedwith the non-conjugated diene.

In the thermoplastic elastomers of the present invention, theabove-mentioned olefin copolymer rubber preferably exists in a partiallycross-linked state, though said copolymer rubber may be present innoncross-linked state, partially cross-linked state and whollycross-linked state.

Besides the above-mentioned olefin copolymer rubbers, other rubbersuseful in the present invention include, for example, diene rubber suchas styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber(NR), butyl rubber (IIR), SEBS, polyisoprene or the like.

In the thermoplastic elastomers used in the invention, the crystallinepolyolefin/rubber weight ratio is 90/10 to 10/90, preferably 70/30 to10/90.

When a combination of the olefin copolymer rubber and other rubber isused as the rubber in the present invention, the other rubber is used ina proportion, based on 100 parts by weight of the sum total of thecrystalline polyolefin and the rubber, of not more than 40 parts byweight, preferably 5-20 parts by weight.

The thermoplastic elastomers preferably used in the present inventioncomprise the crystalline polypropylene and an ethylene/α-olefincopolymer rubber or ethylene/α-olefin/non-conjugated diene copolymerrubber, wherein the crystalline polypropylene and the copolymer rubberare present in a state of being partially cross-linked, and thecrystalline polypropylene/rubber weight ratio is 70/30 to 10/90.

The above-mentioned thermoplastic elastomers may be incorporated, ifnecessary, with such additives as mineral oil softeners, heatstabilizers, antistatic agents, weathering stabilizers, age resistors,fillers, colorants and lubricants.

More concrete examples of the thermoplastic elastomers preferably usedin the invention are those obtained by dynamic heat treatment of amixture (blend) in the presence of organic peroxide, said mixturecomprising 60-10 parts by weight of rubber (b) selected from anethylene/propylene copolymer rubber or an ethylene/propylene/dienecopolymer rubber (the sum total of the components (a) and (b) is 100parts by weight) and 5-100 parts by weight of rubber (c) other than therubber (b) and/or a mineral oil softener (d), and said rubber (b) beingpartially cross-linked.

The organic peroxide used in the dynamic heat treatment above includesconcretely dicumyl peroxide, di-tert-butyl peroxide,2,5-dimethyl-2,5-di-(tert-butylpropoxy)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)hexine-3,1,3-bis(tertbutylproxyisopropyl)benzene,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,n-butyl-4,4-bis(tertbutylperoxy)valerate, benzoyl peroxide,p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butyl perbenzoate, tert-butylperoxyisopropyl carbonate,diacetyl peroxide, lauroyl peroxide, tertbutylcumyl peroxide, etc.

Of these peroxides exemplified above, preferred from the standpoint ofodor and scorch stability are2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane,2,5-dimethyl-2,5-di-(tert-butylperoxy)hexine-3,1,3-bis(tert-butylperoxyisopropyl) benzene,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane andn-butyl-4,4-bis(tert-butylperoxy)valerate, and the most preferred is1,3-bis(tert-butylperoxyisopropyl) benzene.

In the invention, the organic peroxide is used in a proportion, based on100% by weight of the sum total of the crystalline polyolefin andrubber, of 0.05-3% by weight, preferably 0.1-1% by weight.

In practicing the partial cross-linking treatment with theabove-mentioned organic peroxide in accordance with the invention, therecan be used such peroxy linkage assistants as sulfur, p-quinone dioxime,p,p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline,nitrosobenzene, diphenyl guanidine, andtrimethylolpropane-N,N'-m-phenylene dimaleimide, or divinyl benzene,triallyl cyanurate, or such polyfunctional methacrylate monomers asethylene glycol dimethacrylate, diethylene glycol dimethacrylate,polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylateand allyl methacrylate, and functional vinyl monomers such as vinylbutylate and vinyl stearate.

By virtue of the use of the above-exemplified compounds in theabove-mentioned partial cross-linking treatment, a uniform and mildcross-linking reaction can be expected. It is most preferable in theinvention to use particularly divinyl benzene. The preferred divinylbenzene is easy to handle, has good compatibility with the crystallinepolyolefin and rubber which are main components of the material to betreated for cross linkage and acts as a dispersant for the organicperoxide, keeping the cross-linking effect by the heat treatmentuniform, whereby there is obtained a thermoplastic elastomer wellbalanced between flowability and physical properties. The cross-linkingassistants or polyfunctional vinyl monomers mentioned above are usedpreferably in a proportion of 0.1-2% by weight, especially 0.3-1% byweight. If the amount of the cross-linking assistant or polyfunctionalvinyl monomer used exceeds 2% by weight, the cross-linking reactionproceeds excessively fast when the amount of the organic peroxide usedis large and the resulting thermoplastic elastomer is found to be poorin flowability and, on the other hand, when the amount of the organicperoxide is small, the cross-linking assistant or polyfunctional vinylmonomer remains as unaltered monomer in the resulting thermoplasticelastomer, and the thermoplastic elastomer obtained sometimes undergoeschange in physical properties by heat history at the time of fabricationthereof. The cross-linking assistants and polyfunctional vinyl monomersshould not be used in excess.

By "dynamic heat treatment" as used herein is meant that theabove-mentioned components are kneaded together in a molten state.

Kneading devices used for the dynamic heat treatment may be those knownones, for example, open type mixing roll, closed type Banbury mixer,extruder, kneader and continuous mixer. Of these kneading devices, thoseof closed type are preferred, and kneading is preferably carried out inan atmosphere of inert gas such as nitrogen gas or carbonic acid gas.

Furthermore, the kneading is desirably effected at a temperature atwhich a half-life period of the organic peroxide used becomes less than1 minute. The kneading temperature employed is usually 150°-280° C.,preferably 170°-240° C., and the kneading time employed is 1-20 minutes,preferably 3-10 minutes. The shear strength to be applied is selectedfrom among 10-10⁴ sec⁻¹, preferably 10² -10³ sec⁻¹.

The thermoplastic elastomers preferably used in the invention arepartially cross-linked. The expression "partially cross-linked" as usedherein is intended to designate the case wherein the thermoplasticelastomer has the gel content of 20-98% as measured by the followingmethod, and in the invention preferred thermoplastic elastomers arethose having the gel content of 45-98%.

Determination Of Gel Content

About 100 mg of pellets of the thermoplastic elastomer as a sample isweighed into a closed container and immersed for 48 hours at 23° C. in30 ml of cyclohexane which is a sufficient amount for the pellets.

Subsequently, the sample is taken out of the container and placed on afilter paper to dry at room temperature for at least 72 hours until aconstant weight is reached. The gel content of the sample is representedby the following equation.

Gel content %=(dry weight after cyclohexane immersion) /(weight beforecyclohexane immersion)×100

The thermoplastic elastomer (A) from which one layer of the first andsecond thermoplastic elastomer laminates of the invention is composed isexcellent in flowability, because it comprises a crystalline polyolefinand rubber.

Graft-Modified Thermoplastic Elastomer (GA)

The graft-modified thermoplastic elastomer (GA) used in the third andfourth thermoplastic elastomer laminates of the invention includes thoseobtained by dynamic heat treatment and partial crosslinkage of a blendin the presence of organic peroxide, said blend comprising (a) aperoxide crosslinking olefin copolymer rubber, (b) a polyolefin, and (c)α,β-unsaturated carboxylic acid or its derivative, or an unsaturatedepoxy monomer.

The above-mentioned blend herein used may contain (d) a peroxidenon-crosslinking rubbery substance and (e) a mineral oil softener.

The peroxide crosslinking olefin copolymer rubber (a) used in theabove-mentioned blend is an amorphous elastic copolymer derived fromolefins, for example, such as an ethylene/propylene/non-conjugated dienecopolymer rubber or an ethylene/butadiene copolymer rubber, whichdecreases in flowability or will not flow when crosslinked by kneadingin admixture with organic peroxide under application of heat.

The non-conjugated diene contained in theethylene/propylene/non-conjugated diene copolymer rubber mentioned aboveincludes concretely dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene,methylene-norbornene, ethylidene-norbornene, etc.

Of the peroxide crosslinking olefin copolymer rubber (a) mentionedabove, preferably used in the invention are an ethylene/propylenecopolymer rubber or an ethylene/propylene/non-conjugated diene rubberhaving the ethylene component unit/propylene component unit molar ratioof 50/50 to 90/10, particularly 55/45 to 85/15. Of these copolymerrubbers, an ethylene/propylene/non-conjugated diene copolymer rubber,particularly an ethylene/propylene/ ethylidene-norbornene copolymerrubber are preferred, because they are capable of giving thermoplasticelastomers excellent in heat resistant, tensile strength characteristicsand impact resilience.

The peroxide crosslinking olefin copolymer rubbers preferably have aMooney viscosity ML₁₊₄ (100° C.) of 10-250, especially 40-250. When theperoxide crosslinking olefin copolymer rubber having a Mooney viscosityML₁₊₄ (100° C.) of less than 10 is used, the resulting thermoplasticelastomer composition tends to decrease in tensile strengthcharacteristics. On the other hand, when the peroxide crosslinkingolefin copolymer rubber having a Mooney viscosity ML₁₊₄ (100° C.)exceeding 250 is used, the resulting thermoplastic elastomer compositiontends to decrease in flowability.

The peroxide crosslinking olefin copolymer rubbers desirably have aniodine value of not more than 25. When the peroxide crosslinking olefincopolymer rubber having the iodine value as defined above is used, theresulting thermoplastic elastomer is well balanced between flowabilityand rubber properties.

The peroxide crosslinking olefin copolymer rubber (a) is used in aproportion of 95-10 parts by weight, preferably 95-60 parts by weightbased on 100 parts by weight of the total sum of the peroxidecrosslinking olefin copolymer rubber (a) and the polyolefin (b).

When the peroxide crosslinking olefin copolymer rubber (a) is used inthe proportion as defined above, the resulting graft-modifiedthermoplastic elastomer (GA) is excellent in moldability as well as inrubber characteristics such as rubber resilience.

The polyolefin (b) used in the invention is composed of a crystallinehigh molecular weight product obtained by high-pressure or low-pressurepolymerization of at least one monoolefin. Examples of such resin asmentioned above include isotactic or sydiotactic monoolefin polymerresins. Representatives of these resins are commercially available.

Concrete examples of appropriate starting olefins include ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene,3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-octene,1-decene, and mixed olefin containing two or more olefins mentionedabove. In the invention, these starting olefins may be eitherhomopolymerized or copolymerized irrespective of polymerizationtechniques, so long as resinous product is obtained thereby.

Most preferred polyolefins are peroxide decomposing type polyolefins.

By peroxide decomposing type polyolefins as used herein are meantpolyolefins which thermally decompose when mixed with peroxide andkneaded under application of heat, thereby decreasing in molecularweight and increasing in flowability of the resulting resin. Suchpolyolefins include, for example, isotactic polypropylene, copolymers ofpropylene and small amounts of other α-olefin, for example,propylene/ethylene copolymer, propylene/1-butene copolymer,propylene/1-hexene copolymer, propylene/4-methyl-1-pentene copolymer,etc.

The polyolefins used in the invention desirably have a melt index(ASTM-D1239-65T, 23° C.) of 0.1-50, especially 5-20.

The use of the polyolefins contribute toward improvement in flowabilityas well as in heat resistance of the elastomer composition.

The polyolefin (b) is used in a proportion of 5-90 parts by weight,preferably 5-40 parts by weight based on 100 parts by weight of the sumtotal of the peroxide crosslinking copolymer rubber (a) and thepolyolefin (b).

When the polyolefin (b) is used in the proportion as defined above, theresulting graft-modified thermoplastic elastomer (GA) is excellent inrubber characteristics such as rubber resilience and, moreover, inflowability, as a consequence of the foregoing said elastomer (GA) isfound to be excellent in moldability.

The aforesaid α,β-unsaturated carboxylic acid or its derivative, or anunsaturated epoxy monomer (c) is used as a graft modifier.

The above-mentioned α,β-unsaturated carboxylic acid or its derivativeincludes concretely unsaturated carboxylic acids such as acrylic acid,methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconicacid, tetrahydrophthalic acid andbicyclo-[2,2,1]hept-2-ene-5,6-dicarboxylic acid; anhydrides ofunsaturated carboxylic acid such as maleic anhydride, itaconicanhydride, citraconic anhydride, tetrahydrophthalic anhydride, andanhydride of bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid; and estersof unsaturated carboxylic acids such as methyl acrylate, methylmethacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate,dimethyl itaconate, diethyl citraconate, dimethyl anhydroustetrahydrophthalate and dimethylbicyclo[2.2.1]hept-2-ene-5,6-dicarboxylate. Of these compoundsexemplified above, preferred are maleic acid,bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid or anhydride thereof.

The above-mentioned unsaturated epoxy monomer includes concretelyglycidyl ester of unsaturated monocarboxylic acid, such as glycidylacrylate, glycidyl methacrylate or glycidyl p-sterarylcarboxylate;monoglycidyl ester or polyglycidyl ester of such unsaturated carboxylicacid as maleic acid, itaconic acid, citraconic acid, butenetricarboxylicacid, endo-cis-bicylco[2.2.1]hept-5-ene-2,3-dicarboxylic acid, orendo-cis-bicyclo[2.2.1]-hept-ene-2-methyl-2,3-dicarboxylic acid;unsaturated glycidyl ether such as allyl glycidyl ether, 2-methylallylglycidyl ether, glycidyl ether of o-allylphenol, glycidyl ether ofm-allylphenol, glycidyl ether of p-allylphenol, glycidyl ether ofisopropenyl phenol, glycidyl ether of m-biphenol or glycidyl ether ofp-biphenol; 2-(o-vinylphenyl)ethylene oxide, 2-(p-vinylphenyl)ethyleneoxide, 2-(o-vinylphenyl)propylene oxide, 2-(pvinylphenyl)propyleneoxide, 2-(o-allylphenyl)ethylene oxide, 2-(p-allylphenyl)ethylene oxide,2-(o-allylphenyl)propylene oxide, 2-(p-allylphenyl)propylene oxide,p-glycidyl styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene,3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene,vinylcyclohexene monoxide or allyl-2,3-epoxycyclopentyl ether.

The above-mentioned α,β-unsaturated carboxylic acid or its derivative,or an unsaturated epoxy monomer (c) is used in a proportion of 0.01-10parts by weight, preferably 0.1 -5 parts by weight based on 100 parts byweight of the sum total of the peroxide crosslinking olefin copolymerrubber (a) and the polyolefin (c).

When the above-mentioned, α,β-unsaturated carboxylic acid or itsderivative or unsaturated epoxy monomer (c) is used in the proportiondefined above, the resulting graftmodified thermoplastic elastomer (GA)is excellent in moldability and, moreover, excellent in its adhesion tothe ultra-high molecular weight polyolefin layer (B) or the ultra-highmolecular weight polyolefin composition layer (C).

The peroxide non-crosslinking rubbery substance (d) used in theinvention is intended to designate a hydrocarbon rubbery substance whichdoes not cross-link and does not decrease in flowability even when mixedwith peroxide and kneaded under application of heat in the same manneras, for example, in polyisobutylene, butyl rubber, propylene/ethylenecopolymer rubber having the propylene content of at least 70 mol % or atactic polypropylene. Of these, particularly preferred ispolyisobutylene since polyisobutylene is excellent in properties andeasy to handle.

The above-mentioned peroxide non-crosslinking rubber substance (d)contributes toward the improvement in flowability of the elastomercomposition, and particularly preferred are those having a Mooneyviscosity 1+4 (100° C.) of not more than 60.

In the invention, the peroxide non-crosslinking rubbery substance (d) isused in a proportion of 5-100 parts, particularly 5-50 parts by weightbased on 100 parts by weight of the sum total of the peroxidecrosslinking olefin copolymer rubber (a) and the polyolefin (b).

The mineral oil softener (e) used in the invention is a high boilingpetroleum fraction which is usually used for purposes of facilitatingthe roll processing of rubber by weakening intermolecular force ofrubber, of helping dispersion of the filler such as carbon black orwhite carbon or of increasing flexibility or resilience of vulcanizedrubber by decreasing said vulcanized rubber in hardness. The mineral oilsoftener (C) is usually classified as paraffinic, naphthenic andaromatic softeners.

The mineral oil softener (e) is used in a proportion of 3-100 parts byweight, preferably 5-80 parts by weight based on 100 parts by weight ofthe sum total of the peroxide-crosslinking olefin copolymer rubber (a)and the polyolefin (b).

The graft-modified thermoplastic elastomer (GA) used in the invention isprepared by a process which comprises subjecting a blend to dynamic heattreatment in the presence of organic peroxide and thereby to effectpartial crosslinkage, said blend being obtained by mixing together theperoxide-crosslinking olefin copolymer rubber (a), polyolefin (b) andα,β-unsaturated carboxylic acid or its derivative or unsaturated epoxymonomer (c) and, if necessary, the peroxide non-crosslinking rubberysubstance (d) and mineral oil softener (e) in the proportions as definedabove.

It is preferable to use the above-mentioned peroxide non-crosslinkingrubbery substance (d) and mineral oil softener (e).

The graft-modified thermoplastic elastomer (GA) used in the inventionmay be incorporated with fillers and colorants to such an extent that noobjects of the invention are missed.

The fillers used herein include concretely calcium carbonate, calciumsilicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder,asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate,basic magnesium carbonate, molybdeum bisulfide, graphite, glass fiber,glass bead, pumice balloon, carbon fiber, etc.

The colorants used herein include concretely carbon black, titaniumoxide, zinc white, iron oxide red, ultramarine blue, Prussian blue, azopigment, nitroso pigment, lake pigment, phthalocyanine pigment, etc.

The graft-modified thermoplastic elastomer (GA) may further incorporatewith known heat stabilizers such as phenol, sulfite, phenylalkane,phosphite and amine stabilizers; age resistors; weathering agents;antistatic agents; and slip agents such as metallic soap and wax in aproportion commonly employed in the preparation of polyolefins or olefincopolymer rubbers.

The graft-modified thermoplastic elastomer (GA) which has been partiallycross-linked may be prepared by dynamically heat-treating the blendcomprising the above-mentioned components in the presence of organicperoxide.

The term "dynamically heat-treating" is intended to designate that theabove-mentioned components are kneaded together in a molten state.

Preferred examples of the organic peroxide used at the time of thepreparation of the graft-modified thermoplastic elastomer (GA) are thesame as used in the case of the above-mentioned thermoplastic elastomer(A).

The organic peroxide is used in a proportion of 0.05-3% by weight,preferably 0.1-1% by weight based on 100% by weight of the sum total ofthe peroxide cross-linking olefin copolymer rubber (a), polyolefin (b)and α,β-unsaturated carboxylic acid or its derivative or unsaturatedepoxy monomer (c).

When the organic peroxide is used in the proportion as defined above,the resulting graft-modified thermoplastic elastomer (GA) is excellentin rubber properties such as heat resistance, tensile characteristics,elastic recovery and impact resilience, and strength characteristicsand, moreover, excellent in moldability.

Kneading devices and kneading conditions, such as kneading temperature,kneading time and shear force, employed in the preparation of thegraft-modified thermoplastic elastomer (GA) are the same as used in thecase of the thermoplastic elastomer (A).

Peroxy crosslinking assistants, polyfunctional methacrylate monomers andpolyfunctional vinyl monomers which may be used in the above-mentionedpartial cross-linking treatment by means of the organic peroxide are thesame as those used in the case of thermoplastic elastomer (A).

The effects obtained by the use of the above-mentioned crosslinkingassistants and polyfunctional methacrylate monomers are the same as canbe expected in the case of the thermoplastic elastomer (A), and theamounts of these compounds used are the same as in the case of thethermoplastic elastomer (A). In connection with the foregoing, the samedirection for the use of the crosslinking assistants or polyfunctionalvinyl monomers, particularly with respect to amounts of these compoundsto be used, as in the case of the thermoplastic elastomer (A) should bekept, as well.

Furthermore, in order to attain accelerated decomposition of the organicperoxide, there may also be used a decomposition of acceleratorincluding tertiary amine such as triethylamine, tributylamine or2,4,6-tris (dimethylamine)phenol and naphthenate such as aluminum,cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, leador mercury naphthenate.

The graft-modified thermoplastic elastomer used in the invention hasbeen partially cross-linked. The expression "partially cross-linked" asused herein is intended to designate that the elastomer has the gelcontent of 20-98%, preferably 45-98%.

The gel content of the above-mentioned elastomer is obtained by the samemethod employed in the case of the thermoplastic elastomer (A).

The graft-modified thermoplastic elastomer (GA), from which one of thelayers of the third and fourth thermoplastic elastomer laminates of theinvention is formed, is excellent in flowability, because the elastomer(GA) is composed of the partially cross-linked olefin copolymer rubberand polyolefin, particularly the peroxide decomposition type polyolefin.

Ultra-High Molecular Weight Polyolefin (B)

The ultra-high molecular weight polyolefin (B) used in the first andthird thermoplastic elastomer laminates of the invention is alubricating resin which includes, for example, homopolymers orcopolymers of α-olefins such as ethylene, propylene, 1-butene,1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecne, 4-methyl-1-penteneand 3-methyl-1-pentene. Of the polymers mentioned above, preferred inthe invention are ethylene hompolymer and copolymers of ethylene as amajor component and other α-olefins.

Preferably used ultra-high molecular weight polyolefins are those havingan intrinsic viscosity [η], as measured in decalin at 135° C., of 10-40dl/g, particularly 15-35 dl/g.

The ultra-high molecular weight polyolefin (B) may be incorporated withthe same fillers and colorants as used in the aforesaid graft-modifiedthermoplastic elastomer (GA) in like manner.

Furthermore, the ultra-high molecular weight polyolefin (B) used in theinvention may be incorporated with the same additives as used in theaforesaid graft-modified thermoplastic elastomer (GA) in the proportionscommonly employed in the preparation of olefin plastics or olefincopolymer rubbers.

Ultra-High Molecular Weight Polyolefin Composition (C)

The ultra-high molecular weight polyolefin composition (C) used in thesecond and fourth thermoplastic elastomer laminates of the inventioncomprises the ultra-high molecular weight polyolefin having an intrinsicviscosity [η], as measured in decalin at 135° C., of 10-40 dl/g and alow molecular weight or high molecular weight polyolefin having anintrinsic viscosity [η], as measured of 0.1-5 dl/g, said ultra-highmolecular weight polyolefin existing in the composition in a proportionof 15-40% by weight based on 100% by weight of the sum total of theultra-high molecular weight polyolefin and the low molecular or highmolecular weight polyolefin, and said composition having an intrinsicviscosity [η], as measured in decalin at 135° C. of 3.5-8.3 dl/g.

The ultra-high molecular weight polyolefin, from which this composition(C) is formed, is the above-mentioned ultra-high molecular weightpolyolefin (B) having the intrinsic viscosity [η] as mentioned above.

The above-mentioned low molecular or high molecular weight polyolefinother than the ultra-high molecular weight polyolefin in the abovecomposition (C) is a homopolymer or a copolymer of α-olefin such asethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene,1-dodecene, 4-methyl-1-pentene, 3-methyl-1-pentene, etc. In theinvention, an ethylene hompolymer and a copolymer consisting essentiallyof ethylene and other α-olefin are desirably used as the low molecularor high molecular weight polyolefin mentioned above.

The ultra-high molecular weight polyolefin composition (C) may contain1-20% by weight, based on the composition (C), of a liquid or solidlubricant.

The liquid lubricant used in the above composition (C) includes apetroleum lubricating oil and a synthetic lubricating oil.

The petroleum lubricating oil used herein includes concretely liquidparaffin, spindle oil, refrigerator oil, dynamo oil, turbine oil,machine oil, cylinder oil, etc.

The synthetic lubricating oil used herein includes concretely synthetichydrocarbon oil, polyglycol oil, polyphenyl ether oil, ester oil,phosphate ester oil, polychlorotrifluoroethylene oil, fluoroester oil,chlorinated biphenyl oil, silicone oil, etc.

The solid lubricant used mainly in the above composition (C) includesconcretely graphite and molybdenum bisulfide. However, in additionthereto, there may be used boron nitride, tungsten bisulfide, leadoxide, glass powder and metallic soap. The solid lubricant can be usedsingly or in combination with the liquid lubricating oil, for example,the combined lubricant may be added in the form of sol, gel orsuspensoid to the ultra-high molecular weight polyolefin composition.

The above-mentioned ultra-high molecular weight polyolefin composition(C) may be incorporated, if necessary, with additives such as mineraloil softeners, heat stabilizers, antistatic agents, weatheringstabilizers, age resistors, fillers, colorants, slip agents, etc. tosuch an extent that no objects of the invention are missed.

In preparing the thermoplastic elastomer laminates of the invention, theultra-high molecular weight polyolefin composition (C) can be subjectedto co-extrusion laminating treatment with the above-mentionedthermoplastic elastomers [(A) and (GA)], the thermoplastic elastomerlayer and the ultra-high molecular weight polyolefin composition layercan be directly laminated together without requiring the film (sheet)molding process, hence this is economical.

On the one hand, the aforesaid ultra-molecular weight polyoolefin (B)having an intrinsic viscosity [η], as measured in decalin at 135° C., of10-40 dl/g, as it is, cannot be laminated directly with theabove-mentioned thermoplastic elastomer [(A) and (GA)] by co-extrusiontechnique. Accordingly, when the thermoplastic elastomer layer islaminated with the ultra-high molecular weight polyolefin layer, atleast one of these layers must be formed in advance into a film (orsheet), thus this is inferior in economical efficiency to the case ofthe above-mentioned ultra-high molecular weight polyolefin composition(C).

Thermoplastic Elastomer Laminate

The first thermoplastic laminate of the invention is composed of a layerof the above-mentioned thermoplastic elastomer (A) and a layer of theabove-mentioned ultra-high molecular weight polyolefin (B).

The first thermoplastic elastomer laminate of the invention may beobtained by laminating the above-mentioned two layers together.

The thermoplastic elastomer (A) layer (herein after abbreviated to (A)layer) may be laminated with the ultra-high molecular weight polyolefin(B) layer (hereinafter abbreviated to (B) layer) by the followingmethod, though varies according to the shape, size and required physicalproperties of the end product intended and not particularly limited.

(1) A laminating method wherein (A) and (B) layers prepared previouslyare fusion bonded together by means of a calender roll molding machineor compression molding machine at a temperature higher the temperatureat which at least one of the two layers is fused.

(2) A laminating method wherein one of the two (A) and (B) layer isformed in advance into a sheet, and the layer thus formed is then fusionbonded to the other layer under extrusion calender.

In the first thermoplastic laminate of the invention as illustratedabove, the layer composed of the above-mentioned thermoplastic elastomer(A) is excellent in heat resistance, heat aging characteristics andrubber resilience, because said elastomer (A) comprises a crystallinepolyolefin and a rubber.

In the first thermoplastic elastomer laminate of the invention, thelayer composed of the above-mentioned ultra-high molecular weightpolyolefin (B) is excellent in abrasion resistance, scratch resistance,sliding properties and chemical resistance.

The second thermoplastic elastomer laminate of the invention is composedof a layer of the above-mentioned thermoplastic elastomer (A) and alayer of the ultra-high molecular weight polyolefin composition (C).

The second thermoplastic elastomer laminate of the invention may beobtained by laminating the above-mentioned two layers together, and aprocess for obtaining the same is not particularly limited, though itvaries according to the shape, size and required physical properties ofthe final product intended to obtain.

The above-mentioned (A) layer may be laminated to the ultra-highmolecular weight polyolefin composition (C) layer by a laminatingprocess similar to that employed in the case of the first thermoplasticelastomer laminate of the invention.

Furthermore, in preparing the second thermoplastic elastomer laminate ofthe invention, the following laminate method (3) may be employed.

(3) A method wherein (A) layer and (C) layer are coextruded by means ofa multilayer extrusion processing machine to effect the fusion bondingthereof.

In the present invention, a preferred laminating method is theabove-mentioned method (3).

In the second thermoplastic elastomer laminate of the invention, thelayer comprising the above-mentioned thermoplastic elastomer (A) isexcellent in heat resistance, heat aging characteristics and rubberresilience, because said elastomer is composed of a crystallinepolyolefin and a rubber.

Furthermore, in the second thermoplastic elastomer laminate of theinvention, the layer comprising the above-mentioned ultra-high molecularweight polyolefin composition (C) is excellent in abrasion resistance,scratch resistance, sliding properties and chemical resistance.

The third thermoplastic elastomer laminate of the invention is composedof a layer comprising the above-mentioned graft-modified thermoplasticelastomer (GA) and a layer comprising the ultra-high molecular weightpolyolefin (B).

The third thermoplastic elastomer laminate of the invention may beobtained by laminating the above-mentioned two layers together.

In that case, the same laminating methods as in the first thermoplasticelastomer laminate of the invention may be employed therefor

In the third thermoplastic elastomer laminate of the invention, thelayer composed of the above-mentioned graft-modified thermoplasticelastomer (GA) comprising a partially cross-linked olefin copolymerrubber and a polyolefin, preferably a peroxide decomposition typepolyolefin.

In the third thermoplastic elastomer laminate of the invention, thelayer comprising the above-mentioned ultra-high molecular weightpolyolefin (B) is excellent in abrasion resistance, scratch resistance,sliding properties and chemical resistance.

The fourth thermoplastic elastomer laminate of the invention is composedof a layer comprising the above-mentioned graft-modified thermoplasticelastomer (GA) and a layer comprising the ultra-high molecular weightpolyolefin composition (C).

The fourth thermoplastic elastomer laminate of the invention may beobtained by laminating the above-mentioned two layers together.

In that case, the same laminating methods as in the second thermoplasticelastomer laminate of the invention may be employed therefor, andpreferred is the above-mentioned co-extrusion method (3).

In the fourth thermoplastic elastomer laminate of the invention, thelayer composed of the graft-modified thermoplastic elastomer (GA) isexcellent in heat resistance, heat aging characteristics and rubberresilience, because said elastomer (GA) comprising a partiallycross-linked olefin copolymer rubber and a polyolefin, preferably aperoxide decomposition type polyolefin.

Furthermore, in the fourth thermoplastic elastomer laminate of theinvention, the layer comprising the above-mentioned ultra-high molecularweight polyolefin composition (C) is excellent in abrasion resistance,scratch resistance, sliding properties and chemical resistance.

In the first to fourth thermoplastic elastomer laminates of theinvention, it is desirable that the thermoplastic elastomer (A) layerand graft-modified thermoplastic elastomer (GA) layer have a thicknessof 0.1-50 mm, and the ultra-high molecular weight polyolefin (B) layerand ultra-high molecular weight polyolefin composition (C) layer have athickness of 5 μm to 10 mm.

An example of the glass run channels of the present invention isillustrated below in detail with reference to the accompanying drawings

In FIG. 1 showing a sectional structure of an example of the glass runchannel of the invention, this glass run channel comprises a main body 2having a groove-like (U-shaped) cross section and tongue-like drainingportions 3 extending from the tip to the side wall of the groove towardthe central side of said groove This pair of the draining portions 3,3incline to extend inwardly toward the groove of the main body 2, theexterior surface of each draining portion becomes a window contactingportion 4, and points 5,5 of the window glass contacting portions 4 arein such a positioning relationship that they are capable of opening andshutting mutually by themselves. The main body 2 is provided on bothside walls thereof with hooks for fitting the main body 2 with a windowframe.

The main body 2 and draining portions 3,3 are integrally molded from anelastomer. In accordance with the present invention, at least the windowglass containing portions 4,4 are composed of a laminate comprising asubstrate layer comprising the aforesaid thermoplastic elastomer (A) orgraft-modified thermoplastic elastomer (GA) and a lubricating resincomprising the aforesaid ultra-high molecular weight polyolefin (B) orultra-high molecular weight polyolefin composition (C), that is, saidlaminate may be any of the aforesaid first to fourth thermoplasticelastomer laminates of the invention.

As is clear from FIG. 2 showing an enlarged view of this window glasscontacting portion 4, the substrate layer 7 preferably has a roughsurface 8. To this shark skin-like surface 8 is laminated by fusionbonding the above-mentioned lubricating resin layer 9 having a surface10 similar to the surface 8.

In FIGS. 3, 4 and 5 illustrating how this glass run channel is fitted tothe automotive window, the automotive door is provided with a windowglass 12 capable of being opened or shut by means of a vertical motion,and a glass run channel 1 is fastened to a window frame 13. As shown inFIGS. 4 and 5, the window frame 13 is molded so as to have its U-shapedsection as a whole, and inwardly projected portions 15 are formed atinlet parts of a concave portion 14 of the window frame 13. Into thisconcave portion 14 of the window frame 13 is inserted the glass runchannel 1 to engage the hooks 6 of said channel 1 with theabove-mentioned projected portions 15, thereby fixing the glass runchannel 1 to the window frame 13. As shown in FIG. 4, when the windowglass 12 is in a fallen state, the points 5,5 of the glass slidingportions 4,4 are close to each other face to face, and as shown in FIG.5, when the window glass in a state of being elevated, the points 5,5are separated by the window glass 12 inserted between said points 5,5,though the points 5,5 are in contact with the surfaces of the windowglass 12.

In the glass run channel 1 of the invention, at least a portion of saidchannel with which the window glass is brought into contact has thesubstrate layer 7 comprising the aforesaid thermoplastic elastomer (A)or graft-modified thermoplastic elastomer (GA), and the lubricatingresin layer 9 consisting of the aforesaid ultra-high molecular weightpolyolefin (B) or ultra-high molecular weight polyolefin composition (C)fuse-bonded onto the surface of the substrate layer 7.

That is, the above-mentioned thermoplastic elastomers used in theinvention are thermoformable into thermoformed articles of any shape anddimension and, at the same time, they are excellent in characteristicsrequired for the window glass sliding portions of the glass run channelsuch as resilience, flexibility and compressionability and, moreover,excellent in such properties as durability, weathering resistance andwater resistance.

Furthermore, the main body 2 and the substrate layer 7 of the drainingportion 3 of the glass run channel comprising the above-mentionedthermoplastic elastomer are excellent in heat resistance, tensilecharacteristics and rubbery properties such as flexibility and impactresilience. Particularly preferred thermoplastic elastomers used hereinare the above-mentioned partially cross-linked thermoplastic elastomersand partially cross-linked graft-modified thermoplastic elastomers.

The above-mentioned thermoplastic elastomers may be molded into moldedarticles by means of conventional molding devices such as those forcompression molding, transfer molding, injection molding and extrusionprocess.

The aforesaid thermoplastic elastomers (A) and graft-modifiedthermoplastic elastomers (GA) exhibit strong adhesion to the lubricatingresin layer 9 comprising the ultra-high molecular weight polyolefin (B)or ultra-high molecular weight polyolefin composition (C), said resinlayer 9 forming a surface material layer of the substrate layer 7, andare capable of forming by fusion bonding with this lubricating resinlayer 9 laminated structures excellent in interlaminar strengthimmediately after bonding and after the lapse of time, and excellent ininterlaminar strength after weathering test. In the present invention,moreover, the above-mentioned thermoplastic elastomers used for formingthe substrate layer 7 can be molded into molded articles having a sharkskin-like surface, and by combination use of this molding step with thefusion bonding step between the lubricating resin layer 9 and thesubstrate layer 7, this shark skin-like surface pattern can befaithfully reproduced on the outer surface of the lubricating resinlayer 9. According to the conventional coating process using adhesivesas mentioned previously, however, it is extremely difficult to reproducesuch a shark skin-like pattern on the outer surface of the lubricatingresin layer, and this reproduction can only be attained by thecombination use of the above-mentioned molding step and fusion bondingstep.

In accordance with the present invention as illustrated hereinbefore,there can be prepared efficiently glass run channels with the processessmall in number and saved time and labor, while omitting all theprocesses required conventionally such as those of coating the adhesive,of curing or baking the coated adhesive and of embossing the desiredpattern. Furthermore, it has become possible to reduce the frictionalcoefficient between the window glass and the glass run channel byproviding the lubricating resin layer 9 comprising the ultra-highmolecular weight polyolefin (B) or the like as the surface materiallayer of the substrate layer 7. In addition thereto, it has becomepossible to form shark skin-like fine projections uniform in patch onthe outer surface of the lubricating resin layer 9, as compared with theconcave and convex pattern obtained by the conventional embossment.Accordingly, in the glass run channels of the invention, the windowglass can be brought into contact (liquid tight) with the glass runchannel when said window glass is closed and, at the same time, a smoothand light open and close operation of the window glass can be madepossible by reduction in slide friction at the time of opening thewindow glass.

In the glass run channels of the invention, it is desired that thedraining portions 3,3 are formed from the same material used for themain body 2.

When the main body 2 consists of such thermoplastic elastomer asmentioned above, the draining portions 3,3 formed from the same materialas used in the main body 2 are of practical used in point of durabilityas well as in point of bonding strength to the lubricating resin layer9.

Sharkskin (dry or scaly skin)-like pattern useful in the glass runchannels of the invention can be exhibited at the time of molding bysuitably selecting properties of the starting thermoplastic elastomers.

The exterior appearance of the thus obtained sharkskin differs from meltfracture which may be seen at the time of extrusion molding of resins orelastomers, and the molded article having this sharkskin on its surfaceis periodically coarse and has minute projections.

Furthermore, it is necessary that the surface of the lubricating resinlayer 9 laminated to the surface of the sharkskin pattern also has thesame sharkskin pattern exhibited on said surface, and hence thelubricating resin layer 9 is laminated to the surface of the sharkskinpattern to a thickness of usually 3-50 μm. If necessary, the thicknessof the lubricating resin layer 9 may be made either thicker or thinnerthan that defined as above.

The site at which the draining portions 3,3 come in contact with thewindow glass 12 generally varies when the window glass enters or leavessaid site, hence it is desirable that the coating of lubricating resinand, if necessary, the formation of sharkskin pattern be made so as tocover a relatively broad space of the draining portions 3,3.

In the glass run channel shown in FIG. 1, there is indicated a portion16 in side said channel, against which the end of the window glass ishit, and this portion 16 may also be coated on its surface with thelubricating resin layer 9 consisting of the ultra-high molecular weightpolyolefin (B) or the like.

EFFECT OF THE INVENTION

The first to fourth thermoplastic elastomer laminates of the presentinvention are excellent respectively in interlaminar bonding propertiesbetween the thermoplastic elastomer (A) layer and ultra-high molecularweight polyolefin (B) layer, between the thermoplastic elastomer (A)layer and ultra-high molecular weight polyolefin composition (C) layer,between the graft-modified thermoplastic elastomer (GA) layer andultra-high molecular weight polyolefin (B) layer and between thegraft-modified thermoplastic elastomer (GA) layer and ultra-highmolecular weight polyolefin composition (C) layer.

The first to fourth thermoplastic elastomer laminates of the inventionare light in weight in comparison with composite materials consisting ofvulcanized rubber, or nylon fiber of non-rigid PVC, are free fromsurface tackiness caused by exudation of plasticizers or the like and,moreover, excellent in mechanical strength, heat resistance, heat agingcharacteristics, weathering resistance, abrasion resistance, scratchresistance, sliding properties and dimentional stability.

The first to fourth thermoplastic elastomer laminates of the inventionare excellent in economical efficiency, because they can be prepared bya simplified process in comparison with the case of the conventionalcomposite materials as mentioned above. In particular, the thermoplasticelastomer laminates having the ultra high molecular weight polyolefincomposition (C) layer are excellent in economical efficiency more thanthe thermoplastic elastomer laminate having the ultra-high molecularweight polyolefin (B) layer, because the former (laminate) can beprepared by co-extrusion laminating the thermoplastic elastomer (A) withthe ultra-high molecular polyolefin composition (C), or by co-extrusionlaminating the graft-modified thermoplastic elastomer (GA) with theultra-high molecular weight polyolefin composition (C).

The first to fourth thermoplastic elastomer laminates of the inventionhave such effects as mentioned above and can be used not only forapplications in interior automotive trim or sealing materials(particularly glass run channel or belt line mole for which slidingproperties with glass are required) but also for applications infurniture, construction materials, housings for appliances, bags, suitcases, sports goods, office supplies, sundries, etc.

The glass run channels of the invention are excellent in durability,intimate contacting properties with the window glass when it is closed,and in light sliding properties at the time of open-close operation,because the aforesaid thermoplastic elastomer laminates are used in thecontacting portion with the window glass of the glass run channel.

The glass channels of the invention are also excellent in economicalefficiency, because there can be omitted all the steps of coating anadhesive, curing or baking the coated adhesive and of embossingtreatment before or after the above-mentioned steps, with the resultthat the number of processes to be employed can be reduced and theoperating time required can be shortened.

The present invention is illustrated below with reference to examples,but it should be construed that the invention is in no way limited tothose examples

EXAMPLES AND COMPARATIVE EXAMPLE OF LAMINATE Example 1

A mixture of 80 parts by weight of an ethylene/propylene/ethylidenenorbornene copolymer rubber having an ethylene content of 70 mol %, aniodine value of 12 and a Mooney viscosity ML₁₊₄ (100° C.) of 120 (hereinafter abbreviated to "EPDM (1)") and 20 parts by weight of polypropylenehaving MFR (ASTM D 1238-65T, 230° C.) of 13 and a density of 0.91 g/cm³was kneaded in a Banbury mixer in a nitrogen atmosphere at 180° C. for 5minutes. The kneaded product was rolled to obtain a sheet-like productwhich was then formed into square pellets by means of a sheet cutter.

Then, to the thus obtained square pellets, 0.3 part by weight of1,3-bis(tert-butylperoxyisopropyl)benzene (hereinafter abbreviated to"Peroxide (A)") and 0.5 part by weight of divinyl benzene (hereinafterabbreviated to "DVB") were added and mixed in a Henschel mixer.

The resultant mixture was then extruded using a single screw extruderhaving L/D=30 and a screw diameter of 50 mm in a nitrogen atmosphere at220° C., to thereby obtain a thermoplastic elastomer (a).

The gel content of the copolymer rubber in the thermoplastic elastomer(a) was measured by the method mentioned above. The result obtained isshown in Table 1.

Further, the thermoplastic elastomer (a) was compression-molded at 190°C. to prepare a test sheet, on which the physical properties of tensilestress at break (TB), flexibility and moldability were tested accordingto the following methods.

Test Method

(1) Tensile stress at break (TB)

In accordance with JIS K 6301, the tensile stress at break (T_(B) : unitkgf/cm²) was measured at a stress rate of 200 mm/min.

(2) Flexibility

The flexibility was evaluated on the torsional rigidity (unit kgf/cm²)which was measured in accordance with ASTM D 1043.

(3) Moldability

The moldability was evaluated on the melt flow rate (MFR: unit g/10 min,230° C., 2.16 kg) which was measured in accordance with ASTM D 1238.

The thermoplastic elastomer (a) was extruded in the form of a sheet bymeans of a T-die extruder of 50 mm diameter (manufactured and sold byToshiba Machine Co., Ltd.) having a full-flighted screw and a coathangertype T-die under the conditions of L/D=28, 240° C. of an extrusiontemperature and 2.5 m/min of a take-up speed. The extruded sheet-likethermoplastic elastomer (a) in a molten state was laminated on anultra-high molecular weight polyolefin film (trade name: Skived Film of0.1 mm thickness, produced by Sakushin Kogyo K K.). The laminatedmaterial was passed through a pair of rolls in the manner such that theelastomer (a) and the ultra-high molecular weight polyolefin came incontact with the roll at 60° C. and the roll at room temperature,respectively.

Thus, there was obtained a laminate comprising the thermoplasticelastomer (a) layer of 1.0 mm thickness and the ultra-high molecularweight polyolefin layer of 0.1 mm thickness.

The interlaminar bonding strength of the obtained laminate was measuredaccording to the following conditions.

Interlaminar bonding strength test

Test method: Peeling at 180°

Test specimen: 25 mm in width and 100 mm in length

Stress rate: 25 mm/min

Interlaminar bonding strength (unit kgf/cm) is obtained by dividing thepeeling load by the width of the specimen.

The results are shown in Table 1.

Example 2

A thermoplastic elastomer (b) was prepared in the same manner as inExample 1 except that Peroxide (A) and DVB were not used. Using thethermoplastic elastomer (b), a laminate was produced in the same manneras in Example 1. The results are shown in Table 1.

Example 3

A thermoplastic elastomer (c) was prepared in the same manner as inExample 1 except that 10 parts by weight of a butyl rubber IIR-065(degree of unsaturation: 0.8 mol %, produced by Esso, hereinafterabbreviated to "IIR (1)") and 30 parts by weight of a paraffinic processoil (trade name DIANA PROCESS OIL produced by IDEMITSU KOSANN) were usedin addition to EPDM (1) and PP (1). Using the thermoplastic elastomer(c), a laminate was produced in the same manner as in Example 1. Theresults are shown in Table 1.

Example 4

64 parts by weight of ethylene/propylene/ethylidene norbornene copolymerrubber having an ethylene content of 78 mol %, an iodine value of 13 anda Mooney viscosity ML₁₊₄ (100° C.) of 75 (hereinafter abbreviated to"EDPM (2)") which was extended with 40 PHR of paraffinic process oil, 14parts by weight of polypropylene having MFR (ASTM D 1238-65T, 230° C.)of 11 and a density of 0.91 g/cm³ (hereinafter abbreviated to "PP (2)"),14 parts by weight of butyl rubber having a Mooney viscosity ML₁₊₄ (100°C.) of 45 and a degree of unsaturation of 1.0 mol % (hereinafterabbreviated to "IIR (2)"), and 8 parts by weight of paraffinic processoil were kneaded in a Banbury mixer in a nitrogen atmosphere at 180° C.for 5 minutes. The kneaded product was rolled to obtain a sheet-likeproduct which was formed into square pellets by means of a sheet cutter.

Then, the thus obtained square pellets, and a suspension of 0.4 parts byweight of Peroxide (A) in 0.4 parts by weight of DVB were mixed in atumbler mixer to coat the square pellets with the suspension.

The resultant coated pellets were then extruded using an extruder in anitrogen atmosphere at 210° C., to thereby obtain a thermoplasticelastomer (d).

Then, using the thermoplastic elastomer (d), a laminate was produced inthe same manner as in Example 1. The physical properties were measuredin the same manner as in Example 1. The results are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                                                  Property of                                         Properties of thermoplastic elastomer                                                                   laminate                                                      Flexibility               Interlaminar                                        Torsional Moldability                                                                             Gel   bonding                                   T.sub.B   rigidity  MFR       content                                                                             strength                                  [kgf/cm.sup.2 ]                                                                         [kgf/cm.sup.2 ]                                                                         [g/10 min]                                                                              [%]   [kgf/cm]                                  ______________________________________                                        Ex. 1                                                                              85       70        0.5     84    broken                                  Ex. 2                                                                              87       67        0.4     --    broken                                  Ex. 3                                                                              75       55        3.0     70    broken                                  Ex. 4                                                                              50       20        0.5     57    broken                                  ______________________________________                                         Note:                                                                         "broken" means that the substrate is broken.                             

Example 5

The thermoplastic elastomer (a) of Example 1 was extrusion molded at230° C., and at the same time an ultra-high molecular weightpolyethylene composition having an intrinsic viscosity [η], measured indecalin at 135° C., of 7.0 dl/g and a density of 0.965 g/cm³ consistingof 23 parts by weight of ultra-high molecular weight polyethylene havingan intrinsic viscosity [η], measured in decaline at 135° C., of 28 dl/gand 77 parts by weight of low molecular weight polyethylene having anintrinsic viscosity [η], measured in decalin at 135° C., of 0.73 dl/gwas co-extruded on the surface of the thermoplastic elastomer (a).

Thus, there was obtained a laminate comprising the thermoplasticelastomer (a) layer of 1.0 m thickness and the ultra-high molecularweight polyethylene composition layer of 0.1 mm thickness.

The interlaminar bonding strength of the thus produced laminate wasmeasured in the same manner as mentioned above. The result is shown inTable 2.

Example 6

A laminate was produced in the same manner as in Example 5 except thatthe thermoplastic elastomer (b) of Example 2 was used instead of thethermoplastic elastomer (a). The physical properties were measured inthe same manner as mentioned above. The results are shown in Table 2.

Example 7

A laminate was produced in the same manner as in Example 5 except thatthe thermoplastic elastomer (c) of Example 3 was used instead of thethermoplastic elastomer (a). The physical properties were measured inthe same manner as described above. The results are shown in Table 2.

Example 8

A laminate was produced in the same manner as in Example 5 except thatthe thermoplastic elastomer (d) of Example 4 was used instead of thethermoplastic elastomer (a). The physical properties were measured inthe same manner as described above. The results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                                                  Property of                                         Properties of thermoplastic elastomer                                                                   laminate                                                      Flexibility               Interlaminar                                        Torsional Moldability                                                                             Gel   bonding                                   T.sub.B   rigidity  MFR       content                                                                             strength                                  [kgf/cm.sup.2 ]                                                                         [kgf/cm.sup.2 ]                                                                         [g/10 min]                                                                              [%]   [kgf/cm]                                  ______________________________________                                        Ex. 5                                                                              85       70        0.5     84    broken                                  Ex. 6                                                                              87       67        0.4     --    broken                                  Ex. 7                                                                              75       55        3.0     70    broken                                  Ex. 8                                                                              50       20        0.5     57    broken                                  ______________________________________                                         Note:                                                                         "broken" means that the substrate is broken.                             

Example 9

80 parts by weight of EPDM (1) and 20 parts by weight of PP (1) werekneaded in a Banbury mixer in a nitrogen atmosphere at 180° C. for 5minutes. The kneaded product was rolled to obtain a sheet-like productwhich was formed into square pellets by means of a sheet cutter.

Then, to the thus obtained square pellets, 0.3 parts by weight ofPeroxide (A) and 0.5 parts by weight of maleic anhydride (hereinafterabbreviated to "MAH") were added and mixed in a Henschel mixer.

The resultant mixture was then extruded using a single screw extruderhaving L/D=30 and a screw diameter of 50 mm in a nitrogen atmosphere at220° C., to thereby obtain a graft-modified thermoplastic elastomer (e).

The gel content of the copolymer rubber in the graft-modifiedthermoplastic elastomer (e) was measured by the method mentioned above.The result obtained is shown in Table 3.

Further, the graft-modified thermoplastic elastomer (e) wascompression-molded at 190° C. to prepare a test sheet, on which thephysical properties of tensile stress at break (T_(B)), flexibility andmoldability were tested by the methods mentioned above. The results areshown in Table 3.

The graft-modified thermoplastic elastomer (e) was extruded in the formof a sheet by means of T-die extruder of 50 mm diameter (manufacturedand sold by Toshiba Machine Co., Ltd.) having a full-flighted screw anda coathanger type T-die under the conditions of L/D=28, 240° C. of anextrusion temperature and 2.5 m/min of a take-up speed. The sheet-likegraft-modified thermoplastic elastomer (e) extruded in a molten statewas laminated on a film of 0.1 mm thickness of ultra-high molecularweight polyethylene having an intrinsic viscosity [η], measured indecalin at 135° C., of 15 dl/g. The laminated material was passedthrough a pair of rolls in such manner that the graft-modifiedthermoplastic elastomer (e) and the ultra-high molecular weightpolyethylene film came in contact with the roll at 60° C. and the rollat room temperature, respectively.

The interlaminar bonding strength of the thus obtained laminate wasmeasured in the same manner as mentioned above. The result is shown inTable 3.

Further, the dynamic coefficient of friction of the surface of theultra-high molecular weight polyethylene film was measured in thefollowing conditions.

Measurement of the dynamic coefficient of friction:

It is measured using Matsubara type abrasion tester at stepwise.

Abrasion roll material: SUS 304 (degree of roughness of about 6s)

Circumferential speed: 12 m/min

Load: 10 kg

Contact area: 2 cm²

Example 10

A graft-modified thermoplastic elastomer (f) was prepared in the samemanner as in Example 9 except that Peroxide (A) and MAH were used inamounts 0.6 parts by weight and 2.0 parts by weight, respectively. Then,using the graft-modified thermoplastic elastomer (f), a laminate wasproduced in the same manner as in Example 9. The physical propertieswere measured mentioned above. The results are shown in Table 3.

Example 11

A graft-modified thermoplastic elastomer (g) was prepared in the samemanner as in Example 9 except that 10 parts by weight of IIR (1) and 30parts by weight of the paraffinic process oil mentioned above were usedin addition to EPDM (1) and PP (1). Then, using the graft-modifiedthermoplastic elastomer (g), a laminate was produced in the same manneras in Example 9. The physical properties were measured as mentionedabove. The results are shown in Table 3.

Example 12

A graft-modified thermoplastic elastomer (h) was prepared in the samemanner as in Example 11 except that 0.5 parts by weight of glycidylmethacrylate was used instead of 0.5 parts by weight of MAH. Then, usingthe graft-modified thermoplastic elastomer (h), a laminate was producedin the same manner as in Example 11. The physical properties weremeasured as mentioned above. The results are shown in Table 3.

Example 13

A graft-modified thermoplastic elastomer (i) was prepared in the samemanner as in Example 11 except that EPDM (1), PP (1), IIR (1) and theparaffinic process oil were used in amounts of 60 parts by weight, 40parts by weight, 20 parts by weight and 40 parts by weight,respectively. Then, using the graft-modified thermoplastic elastomer(i), a laminate was produced in the same manner as in Example 11. Thephysical properties were measured as mentioned above. The results areshown in Table 3.

Example 14

A graft-modified thermoplastic elastomer (j) was prepared in the samemanner as in Example 11 except that EPDM (1), PP (1), IIR (1) and theparaffinic process oil were used in amounts of 90 parts by weight, 10parts by weight, 20 parts by weight and 40 parts by weight,respectively, and 3 parts by weight of glycidyl methacrylate was usedinstead of 0.5 parts by weight of MAH. Using the thus preparedthermoplastic elastomer (j), a laminate was produced in the same manneras in Example 11. The physical properties measured as mentioned above.The results are shown in Table 3.

Example 15

A graft-modified thermoplastic elastomer (k) was prepared in the samemanner as in Example 11 except that EPDM (1), PP (1), IIR (1), theparaffinic process oil and MAH were used in amounts of 70 parts byweight, 30 parts by weight, 40 parts by weight, 60 parts by weight, and6 parts by weight, respectively. Using the thus prepared thermoplasticelastomer (k), a laminate was produced in the same manner as in Example11. The physical properties measured as mentioned above. The results areshown in Table 3.

Example 16

A laminate was produced in the same manner as in Example 9 except thatthe graft-modified thermoplastic elastomer (e) was extruded at 230° C.,and at the same time an ultra-high molecular weight polyethylenecomposition having an intrinsic viscosity [η], as measured in decalin at135° C., of 5.5 dl/g and a density of 0.955 g/cm³ consisting of 23% byweight of ultra-high molecular weight polyethylene having an intrinsicviscosity [η], as measured in decalin at 135° C., of 30 dl/g and 77% byweight of low molecular weight polyethylene was co-extruded at 250° C.on the surface of the graft-modified thermoplastic elastomer (e). Thus,there was obtained a laminate comprising the thermoplastic elastomer (e)layer of 1.0 mm thickness and the ultra-high molecular weightpolyethylene composition layer of 0.1 mm thickness. The dynamiccoefficient of friction of the ultra-high molecular weight polyethylenecomposition layer in the laminate was 0.15. The results are shown inTable 3.

Comparative Example 1

Substantially the same procedure as in Example 9 was conducted exceptthat a polyamide sheet of 0.1 mm thickness (Trade name: Nylon 6,manufactured by Toray Co., Ltd.) was used instead of the ultra-highmolecular weight polyethylene film, to thereby obtain a laminatecomprising the graft-modified thermoplastic elastomer (e) layer of 1.0mm thickness and the polyamide layer of 0.1 mm thickness. The dynamiccoefficient of friction of the surface of the polyamide layer was 0.8.The results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                        Properties of graft-modified                                                                            Property of                                         polyolefin elastomer      laminate                                                      Flexibility               Interlaminar                              T.sub.B   Torsional Moldability                                                                             Gel   bonding                                   [kgf/     rigidity  MFR       content                                                                             strength                                  cm.sup.2 ]                                                                              [kgf/cm.sup.2 ]                                                                         [g/10 min]                                                                              [%]   [kgf/cm]                                  ______________________________________                                        Ex. 9 85      70        0.5     80    broken                                  Ex. 10                                                                              87      70        0.2     87    broken                                  Ex. 11                                                                              75      55        3.0     70    broken                                  Ex. 12                                                                              78      56        3.0     74    broken                                  Ex. 13                                                                              110     350       27      55    7.0                                     Ex. 14                                                                              57      35        18      56    broken                                  Ex. 15                                                                              87      73        35      46    broken                                  Ex. 16                                                                              85      70        0.5     80    broken                                  Comp. 85      70        0.5     80    broken                                  Ex. 1                                                                         ______________________________________                                         Note:                                                                         "broken" means that the substrate is broken.                             

EXAMPLES OF GLASS RUN CHANNELS

Example 17

75 parts by weight of ethylene/propylene/5-ethylidene-2-norbornenecopolymer rubber having an ethylene content of 70 mol %, an iodine valueof 12 and a Mooney viscosity ML₁₊₄ (100° C.) of 120 and 25 parts byweight of PP (1) were kneaded in a Banbury mixer in a nitrogenatmosphere at 180° C. for 5 minutes. Then, the kneaded product wasrolled to obtain a sheet-like product which was then formed into squarepellets by means of a sheet cutter.

To the thus obtained square pellets, 0.5 part by weight of DVB and 0.3part by weight of Peroxide (A) were added and stirred in a Henshelmixer.

Then, the resultant mixture was extruded using a single screw extruderhaving L/D=30 and a screw diameter of 50 mm in a nitrogen atmosphere at220° C., to thereby obtain a thermoplastic elastomer (1).

The gel content of the thermoplastic elastomer (1) was 97% by weightmeasured by the above-mentioned method.

The thermoplastic elastomer (1) was extruded at 230° C. to form a glassrun channel comprising a main body and draining portions, and at thesame time a film of 0.1 mm thickness of ultra-high molecular weightpolyethylene having an intrinsic viscosity [η], as measured in decalinat 135° C., of 15 dl/g, which was preheated at 90° C., was laminated onthe surface of the glass run channel by heat-fusion bonding in theoutlet of the mold to thereby obtain the glass run channel of thepresent invention.

The cross-section view of the obtained glass run channel was as shown inFIG. 1. The glass run channel had an approximately trapezoidal shape.The total length of the inclined portion and horizontal portion of theglass run channel 1, to be fastened to the window frame 13, was 1500 mmand the length of the vertical portion was 90 mm, as shown in FIG. 3.The outside width of the bottom portion of the main body 2 was 15 mm,the height of the outside of the side portion was 20 mm and the lengthof the draining portions 3 was 10 mm as shown in FIG. 1. The thicknessof the ultra-high molecular weight polyethylene composition layer was 30μm on an average.

The molding time of the glass run channel could be shortened by 0.2min/m as compared to that of a conventional method, that is, the moldingtime was decreased to 60% of the molding time of the conventionalmethod.

The obtained glass run channel was fastened to a test window frame and awindow glass of 3.2 mm thickness was provided therein. The durabilitytest of the glass run channel was effected in the manner such that thewindow glass was repeatedly opened and closed. As a result, it was foundthat the glass run channel had an excellent durability without injuringthe function as the glass run channel after repeating 50,000 timesopen-close operation. On the other hand, the conventional glass runchannel having a laminate structure such that the window glass slidingportion was made by bonding a nylon film to a non-rigid polyvinylchloride resin layer was worn out at the contact surface with the windowglass after repeating 25,000 times open-close operation, that is, thefrictional resistance was extremely increased therebetween, andtherefore such conventional glass run channel could not be used.

Example 18

75 parts by weight of ethylene/propylene/ethylidene norbornene copolymerrubber of Example 17 and 25 parts by weight of PP (1) were kneaded in aBanbury mixer in a nitrogen atmosphere at 180° C. for 5 minutes. Then,the kneaded product was rolled to obtain a sheet-like product which wasthen formed into square pellets by means of a sheet cutter.

To the thus obtained square pellets, 0.5 part by weight of DVB and 0.3part by weight of Peroxide (A) were added and stirred in a Henschelmixer.

Then, the resultant mixture was extruded using a single screw extruderhaving L/D=30 and a screw diameter of 50 mm in modified thermoplasticelastomer (m).

The gel content of the graft-modified thermoplastic elastomer (m) was96% by weight measured by the above-mentioned method.

The graft-modified thermoplastic elastomer (m) was molded in the samemanner as in Example 17, to thereby obtain a glass run channel. Themolding time was decreased to 60% of the molding time of theconventional method. The durability test was effected in the same manneras in Example 17. As a result, it was found that the glass run channelof the present invention had an excellent durability after repeating50,000 times open-close operation.

Example 19

The thermoplastic elastomer (1) of Example 17 was extruded at 230° C. toform a glass run channel comprising a main body and draining portions,and at the same time a film of 0.1 mm thickness of ultra-high molecularweight polyethylene composition having an intrinsic viscosity [η], asmeasured in decalin at 135° C., of 7.0 dl/g and a density of 0.965g/cm³, which is consisting of 23% by weight of ultra-high molecularweight polyethylene having an intrinsic viscosity [η], as measured indecalin at 135° C., of 28 dl/g and 77% by weight of low-molecular weightpolyethylene having an intrinsic viscosity [η], as measured in decalinat 135° C., of 0.73 dl/g was laminated on the surface of the glass runchannel by co-extrusion, to thereby obtain the glass channel of thepresent invention.

The cross-section view of the obtained glass run channel was as shown inFIG. 1. The glass run channel had an approximately trapezoidal shape.The total length of the inclined portion and horizontal portion of theglass run channel 1, to be fastened to the window frame 13, was 1500 mmand the length of the vertical portion was 90 mm as shown in FIG. 3. Theoutside width of the bottom portion of the main body 2 was 15 mm, theoutside height of the side portion was 20 mm and the length of thedraining portion 3 was 10 mm as shown in FIG. 1. The thickness of theultra-high molecular weight polyethylene composition layer was 30 μm onan average.

The molding time of the glass run channel could be shortened by 0.2min/m as compared to that of a conventional method, that is, the moldingtime was decreased to 60% of the molding time of the conventionalmethod.

The obtained glass run channel was fastened to a test window frame and awindow glass of 3.2 mm thickness was provided therein. The durabilitytest of the glass run channel was effected in the manner such that thewindow glass was repeatedly opened and closed. As a result, it was foundthat the glass run channel had an excellent durability without injuringthe function as the glass run channel after repeating 50,000 timesopen-close operation. On the other hand, the conventional glass runchannel having a laminate structure such that the window glass slidingportion was made by bonding a nylon film to a non-rigid polyvinylchloride resin layer was worn out at the contact surface with the windowafter repeating 25,000 times open-close operation, that is thefrictional resistance was extremely increased therebetween, andtherefore such glass run channel could not be used.

Example 20

An ultra-high molecular weight polyethylene composition was prepared inthe same manner as in Example 19 except that instead of the ultra-highmolecular weight polyethylene high molecular weight polyethylenecomposition and 2 parts by weight of ethylene/propylene copolymersynthetic oil having a number average molecular weight of 1300 and adynamic friction of 100 cSt at 100° C., as a liquid lubricant, werestirred in a Henschel mixer and pelletized by a monoaxial extruder.

Then, using the thus prepared ultra-high molecular weight polyethylenecomposition, a glass run channel was produced in the same manner as inExample 19.

The molding time of the glass run channel was decreased to 60% of thatof a conventional method. The glass run channel had an excellentdurability without injuring the function as the glass run channel afterrepeating 50,000 times open-close operation.

A glass run channel was produced in the same manner as in Example 19except that the graft-modified thermoplastic elastomer (m) of Example 18was used instead of the thermoplastic elastomer (1).

The molding time of the glass channel run channel was decreased to 60%of that of a conventional method. The glass run channel had an excellentdurability without injuring the function as the glass run channel afterrepeating 50,000 times open-close operation.

We claim:
 1. A thermoplastic elastomer laminate which comprises a layercomprising a thermoplastic elastomer (A) composed of a crystallinepolyolefin and a rubber, anda layer comprising an ultra-high molecularweight polyolefin (b), wherein said thermoplastic elastomer (A) isobtained by subjecting a mixture comprising70-10 parts by weight of acrystalline polyolefin (a) and (30-90 parts by weight of a rubber (b)which is an ethylene/propylene copolymer rubber or anethylene/propylene/diene copolymer, the sum total of the components (a)and (b) is 100 parts by weight, to dynamic heat treatment in thepresence of an organic peroxide, said rubber (b) being partiallycross-linked.
 2. The thermoplastic elastomer laminate according to claim1 wherein said ultra-high molecular weight polyolefin (B) has anintrinsic viscosity [η], as measured in decalin at 135° C., of 10-40dl/g.
 3. A thermoplastic elastomer laminate which comprisesa layercomprising a thermoplastic elastomer (A) composed of a crystallinepolyolefin and a rubber, and a layer comprising an ultra-high molecularweight polyolefin composition (C), said ultra-high molecular weightpolyolefin composition (C) consisting essentially of an ultra-highmolecular weight polyolefin having an intrinsic viscosity [η], asmeasured in decalin at 135° C., of 10-40 dl/g, and a polyolefin havingan intrinsic viscosity [η], as measured in decalin at 135° C., of 0.1-5dl/g, said ultra-high molecular weight polyolefin existing in aproportion of 15-40% by weight based on 100% by weight of the sum totalof the ultra-high molecular weight polyolefin and polyolefin, and saidultra-high molecular weight polyolefin composition (C) having anintrinsic viscosity [η], as measured in decalin at 135° C., of 3.5-8.3dl/g.
 4. The thermoplastic elastomer laminate according to claim 3wherein said thermoplastic elastomer (A) is obtained by subjecting amixture comprising70-10 parts by weight of a crystalline polypropylene(a) and 30-90 parts by weight of a rubber (b) which is anethylene/propylene copolymer rubber or an ethylene/propylene/dienecopolymer rubber (the sum total of the components (a) and (b) is 100parts by weight) to dynamic heat treatment is the presence of an organicperoxide, said rubber (b) being partially cross-linked.
 5. Thethermoplastic elastomer laminate according to claim 3 wherein saidultra-high molecular weight polyolefin composition (c) contains 1-20% byweight, based on the composition (c), of a liquid or solid lubricant. 6.A thermoplastic elastomer laminate which comprisesa layer comprising athermoplastic elastomer (a) composed of a crystalline polyolefin and arubber, and a layer comprising an ultra-high molecular weight polyolefincomposition (C), said ultra-high molecular polyolefin composition (C)consisting essentially of an ultra-high molecular weight polyolefinhaving an intrinsic viscosity [η], as measured in decalin at 135° C., of10-40 dl/g, and a polyolefin having an intrinsic viscosity [η], asmeasured in decalin at 135° C., of 0.1-5 dl/g, said ultra-high molecularweight polyolefin existing in a proportion of 15-40% by weight based on100% by weight of the sum total of the ultra-high molecular weightpolyolefin and polyolefin, and said ultra-high molecular weightpolyolefin composition (C) having an intrinsic viscosity [η], asmeasured in decalin at 135° C., of 3.5-8.3 dl/g. wherein saidthermoplastic elastomer (A) is obtained by subjecting a mixturecomprising 70-10 parts by weight of a crystalline polypropylene (a) and30-90 parts by weight of a rubber (b) which is an ethylene/propylenecopolymer rubber or an ethylene/propylene/diene copolymer rubber the sumtotal of the components (a) and (b) being partially cross-linked.
 7. Thethermoplastic elastomer laminate according to claim 6 wherein saidultra-high molecular weight polyolefin composition (C) contains 1-20% byweight, based on the composition (C), of a liquid or solid lubricant.